Oxygen promoted radical polymerization of acrylonitrile in aqueous nitric acid. A kinetic study

The polymerization of acrylonitrile (AN) initiated by oxygen-ascorbic acid (AA)-ferric ion system was studied in dil. HNO₃ at 40°. The rate of polymerization, R_p, was found gravimetrically. In the [Fe³⁺] range, (2–5 × 10^?5 M, R_p was proportional to [AN]^{1.5 ± 0.05}, [O₂]^{0.5 ± 0.02} [AA]⁰ and [Fe³⁺]⁰; for [Fe³⁺] = (5–30) × 10^?5 M, it was proportional to [AN]^{1.8 ± 0.05}, [O₂]^{0.6 ± 0.02}, [AA]⁰ and [Fe³⁺]^{?0.9 ± 0.05}. A plausible reaction scheme is proposed and rate law presented to explain these results. R_p increased with ionic strength and [HNO₃] (up to ～0.25 M). An initial rate increase with temperature followed by a decrease was noticed. Chain lengths of the polymers were determined viscometrically.     

An efficient synthesis of (+)-prelactone B

An enantioselective synthesis of (+)-prelactone B 1 has been achieved on a multigram scale starting from a known bicyclic precursor 2. The key feature of the strategy is the generation of 3-stereogenic centres from a single bicyclic precursor, which has been utilized as a chiral building block for the synthesis of various natural products.     

Solvent extraction of cobalt/II/with 2,4-dihydroxyacetophenone thiosemicarbazone

The extraction of cobalt/II/ from ammonium chloride-ammonium hydroxide buffer solutions of pH 6.5 by 2,4-dihydroxyacetophenone thiosemicarbazone /DATS/ in n-butanol has been studied. Cobalt/II/ forms 11 complex /metal:reagent/ with DATS. Addition of pyridine enhances the extraction. The influence of metal concentration and the effect of diverse ions on the extraction of cobalt/II/ have been investigated.     

Bond dissociation energies and bond orders for diatomic alkali halides

The bond dissociation energies for Alkali halides have been estimated based on the derived relations: $$\begin{gathered} D_{AB} = \bar D_{AB} + 31.973{\text{ e}}^{0.363\Delta x} {\text{ and}} \hfill \\ D_{AB} = \bar D_{AB} (1 - 0.2075\Delta xr_e ) + 52.29\Delta x, \hfill \\ \end{gathered} $$ where \(\bar D_{AB} = (D_{AA} \cdot D_{BB} )^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} \) , Δx represents Pauling electronegativity differences x(_A ?x_B) and r _e is the internuclear distance. A simplified formula relating bond orders, q, to spectroscopic constants is suggested. The formula has the form q = 1.5783 × 10^?3 (ω _e ² r_e/ B_e)^1/2. The ambiguity arising from the Parr and Borkman relation is discussed. The present study supports the view of Politzer that q/(0.5r _e)² is the correct definition of bond order. The estimated bond energies and bond orders are in reasonably good agreement with the literature values. The bond energies estimated with the relations we suggested, for alkali halides give an error of 4.5% and 5.3%, respectively. The corresponding error associated with Pauling's equation is 40.2%.     

Structural characterization of CeO(2)-ZrO(2)/TiO(2) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) mixed oxide catalysts by XRD, Raman spectroscopy, HREM, and other techniques

Structural characteristics of CeO(2)-ZrO(2)/TiO(2) (CZ/T) and V(2)O(5)/CeO(2)-ZrO(2)/TiO(2) (V/CZ/T) mixed oxide catalysts have been investigated using X-ray diffraction (XRD), BET surface area, Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HREM) techniques. The CeO(2)-ZrO(2) (1:1 mole ratio) solid solution was deposited over a finely powdered TiO(2) support by a deposition precipitation method. A nominal 5 wt % V(2)O(5) was impregnated over the calcined (773 K) CZ/T mixed oxide carrier by a wet impregnation technique. The obtained CZ/T and V/CZ/T samples were further subjected to thermal treatments from 773 to 1073 K to understand the dispersion and temperature stability of these materials. In the case of CZ/T samples, the XRD results suggest the formation of different cubic and tetragonal Ce-Zr-oxide phases, Ce(0.75)Zr(0.25)O(2), Ce(0.6)Zr(0.4)O(2), Ce(0.5)Zr(0.5)O(2), and Ce(0.16)Zr(0.84)O(2) in varying proportions depending on the treatment temperature. With increasing calcination temperature from 773 to 1073 K, the intensity of the lines pertaining to cubic Ce(0.6)Zr(0.4)O(2) and Ce(0.5)Zr(0.5)O(2) phases increased at the expense of cubic Ce(0.75)Zr(0.25)O(2), indicating more incorporation of zirconia into the ceria lattice. The TiO(2) was mainly in the anatase form whose crystallite size also increased with increasing treatment temperature. A better crystallization and more incorporation of zirconia into the ceria lattice was noted when CZ/T was impregnated with V(2)O(5). However, no crystalline V(2)O(5) could be seen from both XRD and RS measurements. In particular, a preferential formation of CeVO(4) compound and an intense tetragonal Ce(0.16)Zr(0.84)O(2) phase were noted beyond 873 K. The HREM results indicate, in the case of CZ/T samples, a well-dispersed Ce-Zr-oxide of the size approximately 5 nm over the bigger crystals ( approximately 40 nm) of TiO(2) when treated at 873 K. The exact structural features of these crystals as determined by digital diffraction analysis of experimental images reveal that the Ce-Zr-oxides are mainly in the cubic fluorite geometry and the TiO(2) is in anatase form. A better crystallization of Ce-Zr-oxides ( approximately 8 nm) over the surface of bigger crystals of TiO(2) was noted at 1073 K. A further enhancement in the crystallite size and zirconia-rich tetragonal phase was noted in the case of V/CZ/T samples. Further, the structure of CeVO(4) formed was also clearly identified in conformity with XRD and RS results.     

Synthesis and antispasmodic activity evaluation of bis-(papaverine) analogues

A new series of N-substituted bis-(tetrahydropapaverine) ring systems have been synthesised in expectation of better antispasmodic activity in comparison with papaverine. The synthesis of the targeted heterocycles is described along with a discussion of their structure activity relationship. The general synthetic methods of bis-(tetrahydropapaverine) analogues involve tetrahydropapaverine, various piperazines, diisocyanates and diisothiocyanates as starting materials. Pharmacological evaluation involves the in vitro antispasmodic activity on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, N,N'-bis-[2-carbamoyl-1-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolinyl]piperazine (22), was found to be the most potent muscle relaxant (IC(50): 0.31 microM).     

A new route to obtain shape-controlled gold nanoparticles from Au(III)-beta-diketonates

Ligands with a beta-diketone skeleton have been employed for the first time as reductant to produce ligand stabilized gold nanoparticles of different shapes from aqueous HAuCl(4) solution. Evolution of stable gold nanoparticles follows first order (k approximately equal to 10(-2) min(-1)) kinetics with respect to Au(0) concentration. Growth of particles of different shapes (spherical or triangular or hexagonal) goes hand in hand under the influence of different beta-diketones, which have excellent capping and reducing properties. Chlorine insertion was observed to take place in the beta-diketone skeleton.     

Expedient, stereocontrolled synthesis of (+)-compactin lactone via intramolecular Reformatsky reaction

A concise, stereodefined synthesis of compactin lactone is described. Samarium(II) iodide mediated intramolecular Reformatsky reaction is the key step in the synthesis.     

Microwave-assisted solid-phase synthesis of peptoids

Microwave irradiation reduces the reaction time for the solid-phase synthesis of peptoids. Under these conditions, coupling of each residue requires only 1 min. The purity and yields of peptoids synthesized in this way are as good as or better than those achieved using standard methods. [reaction: see text]     

Mixed-ligand chelate extraction of neodymium(III) with thenoyltrifluoroacetone and various sulphoxides

Mixed-ligand chelate extraction of Nd(III) into benzene with mixtures of thenoyltrifluoroacetone (HTTA) and bis-2-ethylhexyl sulphoxide (B2EHSO) or di-n-octyl sulphoxide (DOSO) or diphenyl sulphoxide (DPhSO) or trioctylphosphine oxide (TOPO) from thiocyanate solutions has been studied. A very high synergistic enhancement of the order 10(3) has been observed in these systems. Thus this mixed-ligand chelate system may be useful in the extraction and separation of Nd(III) from other metal ions. The mechanism of extraction can be explained by a simple chemically based model presented in this paper.